Abstract

The electronic spectrum of a cold molecular beam of zirconium dioxide, ZrO2, has been investigated using laser induced fluorescence(LIF) in the region from 17 000 cm−1 to 18 800 cm−1 and by mass-resolved resonance enhanced multi-photon ionization (REMPI) spectroscopy from 17 000 cm−1–21 000 cm−1. The LIF and REMPI spectra are assigned to progressions in the (ν1, ν2, ν3) ← (0, 0, 0) transitions. Dispersed fluorescence from 13 bands was recorded and analyzed to produce harmonic vibrational parameters for the state of ω1 = 898(1) cm−1, ω2 = 287(2) cm−1, and ω3 = 808(3) cm−1. The observed transition frequencies of 45 bands in the LIF and REMPI spectra produce origin and harmonic vibrational parameters for the state of Te = 16 307(8) cm−1, ω1 = 819(3) cm−1, ω2 = 149(3) cm−1, and ω3 = 518(4) cm−1. The spectra were modeled using a normal coordinate analysis and Franck-Condon factor predictions. The structures, harmonic vibrational frequencies, and the potential energies as a function of bending angle for the and states are predicted using time-dependent density functional theory, complete active space self-consistent field, and related first-principle calculations. A comparison with isovalent TiO2 is made.

Received 08 July 2011Accepted 12 August 2011Published online 08 September 2011

Acknowledgments:

The work at Arizona State University was supported by grants from the Fundamental Interactions Branch, Division of Chemical Sciences, Office of Basic Energy Sciences, Department of Energy DE-FG02–01ER15153-A003), and that in Basel by the Swiss National Science Foundation (Project No. 200020–124349/1).